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At least 19 records

Molecular View on Mechanical Reinforcement in Polymer Nanocomposites

The microscopic origin of mechanical enhancement in polymer nanocomposite (PNC) melts is investigated through the combination of rheology and small-angle neutron scattering. It is shown that in the absence of an extensive particle network, the molecular deformation of polymer chains dominates the stress response on intermediate time scales. Quantitative analyses of small-angle neutron scattering spectra, however, reveal no enhanced structural anisotropy in the PNCs, compared with the pristine polymers under the same deformation conditions. These results can demonstrate that the mechanical reinforcement of PNCs is not due to molecular overstraining, but instead a redistribution of strain field in the polymer matrix, akin to the classical picture of hydrodynamic effect of nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailored Silicone Network Architecture for Ultimate Mechanical Reinforcement

Hydrosilylation cured silicone elastomers are subject to reaction inefficiency, leading to incomplete and non-uniform crosslink networks, restricting the potential of mechanical reinforcement. This work investigates pre-synthesized, functional PDMS architectures as additives to improve ultimate mechanical performance relative to conventional single-step curing. Three custom, functional structures were prepared: a partially crosslinked PDMS scaffold (Structure A), a bottle-brush PDMS (Structure B), and a star-shaped PDMS derived from an MQ resin (Structure C). Rheological characterization was used to identify the ultimate design space and proper stoichiometric ratio for Structure A, and confirm successful formation of all structures for suitable incorporation into a base silicone formulation at 30wt%. Mechanical tests indicated that all three structures increased in ultimate tensile strength relative to their single-step counterparts, with Structure A providing additional improvements to toughness (432 vs. 258 kJ/m3) and ultimate elongation (158 vs. 115%). Furthermore, Structure B remained very soft in the unfilled state, while Structure C provided hardness (23 vs. 18 Shore A) and stiffness (780 vs. 420 kPa Young’s modulus) increases. In silica filled systems, Structure A retained increased strength but reduced elongation, while Structure B indicated strong reinforcement in terms of strength, toughness, and stiffness. Thermal analysis on the cure profiles of these materials suggested that pre-formation of network architectures enable a more complete reaction than a single-step process (15.9 vs. 15.1 J/g). Ultimately, these results indicate that tailoring PDMS architecture before the final cure can improve ultimate mechanical properties via improved network development in silicone elastomers. Furthermore, this work offers a promising strategy for designing higher-performance, more tunable silicone formulations.

36 MATERIALS SCIENCE↗

In situ mechanical reinforcement of polymer hydrogels via metal-coordinated crosslink mineralization

Biological organic-inorganic materials remain a popular source of inspiration for bioinspired materials design and engineering. Inspired by the self-assembling metal-reinforced mussel holdfast threads, we tested if metal-coordinate polymer networks can be utilized as simple composite scaffolds for direct in situ crosslink mineralization. Starting with aqueous solutions of polymers end-functionalized with metal-coordinating ligands of catechol or histidine, here we show that inter-molecular metal-ion coordination complexes can serve as mineral nucleation sites, whereby significant mechanical reinforcement is achieved upon nanoscale particle growth directly at the metal-coordinate network crosslink sites.

36 MATERIALS SCIENCE↗

In‐Scribe Silane Bonding for Mechanical Reinforcement of Perovskite Photovoltaic Modules

Despite the extraordinary rise in power conversion efficiency over the last decade, metal halide perovskite (MHP) photovoltaics remain more mechanically fragile than other PV technologies. In this work, the scribe area, created by the monolithic interconnection of thin-film solar cells, is used to extrinsically reinforce the mechanical robustness of packaged MHP solar modules. In contrast to the epoxy-based chemistries often leveraged in the MHP literature, silane-grafted polyolefin encapsulants are designed to form strong covalent bonds to oxide surfaces, specifically to glass and the transparent conductive oxide at the base of the scribe line. Pseudo-modules encapsulated with silane-grafted polyolefin are measured with more than an order-of-magnitude enhancement infracture energy from 0.27 ± 0.01 J·m −2 (no scribes) to 5.97 ± 0.42 J·m −2 (scribes perpendicular to delamination directioncovering ≈2.2% of the module area). The silane-grafted polyolefin retains strong adhesion even after undergoing an accelerated IEC 61215 thermal cycling test consisting of 250 cycles. We find that the in-scribe bonding allows perovskite modules to have adhesion strength comparable to commercial c-Si and CdTe technologies with only 5% reduction in the active module area. This manufacturing-compatible approach offers a practical solution to address the mechanical integrity challenges in MHP solar modules, regardless of cell architecture.

14 SOLAR ENERGY↗

Turning Rubber into a Glass: Mechanical Reinforcement by Microphase Separation

Supramolecular associations provide a promising route to functional materials with properties such as self-healing, easy recyclability or extraordinary mechanical strength and toughness. The latter benefit especially from the transient character of the formed network, which enables dissipation of energy as well as regeneration of the internal structures. However, recent investigations revealed intrinsic limitations in the achievable mechanical enhancement. Here we present studies of a set of telechelic polymers with hydrogen-bonding chain ends exhibiting an extraordinarily high, almost glass-like, rubbery plateau. This is ascribed to the segregation of the associative ends into clusters and formation of an interfacial layer surrounding these clusters. An approach adopted from the field of polymer nanocomposites provides a quantitative description of the data and reveals the strongly altered mechanical properties of the polymer in the interfacial layer. These results demonstrate how employing phase separating dynamic bonds can lead to the creation of high-performance materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanically Reinforced Pseudosolid Polyelectrolyte Membranes via Layer-by-Layer Assembly for High-Performing Lithium-Metal Batteries

Ionogels are emerging as high-potential pseudosolid electrolytes for lithium-metal batteries (LMBs), leveraging their intrinsic high ionic conductivity from entrapped ionic liquid (IL) electrolytes. However, their practical application is hindered by poor mechanical strength stemming from the confinement of ILs within a polymer matrix. To address this challenge, the formation of conformal polyion coatings with functional groups is reported to be relevant to LMBs’ application on ionogels, utilizing a layer-by-layer (LbL) assembly strategy. Here, this approach significantly enhances the mechanical strength (Young's modulus and tensile strength) and electrochemical performance of ionogels, owing to the tailored interface modifications introduced by functional groups’ specific conformal polyion coatings. The core of this methodology leverages the inherent ionic structure of ionogels to enable facile interface modification through Coulombic interactions between polyanions and polycations. These conformally coated interface functionalized membranes show improved electrochemical performance when integrated with cathode materials such as LiFePO 4 (LFP) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) in an LMB configuration, underscoring their potential for robust, high-conductivity, pseudosolid membranes for LMB applications. These innovative pseudosolid membranes offer improved mechanical and electrochemical properties, leading to higher battery efficiency and safety, making them promising candidates for next-generation LMB technology.

25 ENERGY STORAGE↗

3D Ion-Conducting, Scalable, and Mechanically Reinforced Ceramic Film for High Voltage Solid-State Batteries

Concerning the safety aspects of Li+ ion batteries, an epoxy-reinforced thin ceramic film (ERTCF) is prepared by firing and sintering a slurry-casted composite powder film. The ERTCF is composed of Li + ion conduction channels and is made of high amounts of sintered ceramic Li 1+ x Ti 2-x Al x (PO 4 ) 3 (LATP) and epoxy polymer with enhanced mechanical properties for solid-state batteries. The two- and three-dimensional characterizations are conducted not only for showing continuous Li+ ion channels thorough LATP ceramic channels with over 10-4 S cm-1 of ionic conductivity but also to investigate small amounts of epoxy polymer with enhanced mechanical properties. Solid-state Li + ion cells are fabricated using the ERTCF and they show initial charge–discharge capacities of 139/133 mAh g -1 . Furthermore, the scope of the ERTCF is expanded to high-voltage (>8 V) solid-state Li + ion batteries through a bipolar stacked cell design. Hence, it is expected that the present investigation will significantly contribute in the preparation of the next generation reinforced thin ceramic film electrolytes for high-voltage solid-state batteries.

25 ENERGY STORAGE↗

Dual–Interface–Reinforced Flexible Perovskite Solar Cells for Enhanced Performance and Mechanical Reliability

Two key interfaces in flexible perovskite solar cells (f-PSCs) are mechanically reinforced simultaneously: one between the electron-transport layer (ETL) and the 3D metal-halide perovskite (MHP) thin film using self-assembled monolayer (SAM), and the other between the 3D-MHP thin film and the hole-transport layer (HTL) using an in situ grown low-dimensional (LD) MHP capping layer. The interfacial mechanical properties are measured and modeled. This rational interface engineering results in the enhancement of not only the mechanical properties of both interfaces but also their optoelectronic properties holistically. As a result, the new class of dual-interface-reinforced f-PSCs has an unprecedented combination of the following three important performance parameters: high power-conversion efficiency (PCE) of 21.03% (with reduced hysteresis), improved operational stability of 1000 h T90 (duration at 90% initial PCE retained), and enhanced mechanical reliability of 10 000 cycles n88 (number of bending cycles at 88% initial PCE retained). Furthermore, the scientific underpinnings of these synergistic enhancements are elucidated.

14 SOLAR ENERGY↗

General H2O Outgassing Model Applicable to Silica-Filled Silicones

Moisture-induced agining and degradation are continuing concerns in long-term storage and use of silicone materials. The silica fillers frequently used to provide mechanical reinforcement in silicone formulations have a high affinity for H2O and act as a source of moisture outgassing later when placed in dry or vacuum applications.

36 MATERIALS SCIENCE↗

Revealing the Crystalline Architecture of Semicrystalline Ion Exchange Membranes for the Design of Conductive and Durable Alkaline Anion Exchange Membranes

Alkaline anion exchange membrane (AAEM) fuel cells offer a cost-effective alternative to proton exchange membrane (PEM) fuel cells by eliminating the need for expensive precious metal catalysts. In both PEMs and AAEMs, semicrystalline polymers are a common choice, as the crystalline domains can act as mechanical reinforcements that limit swelling and promote mechanical durability in the material. However, spatially resolved characterization of crystalline organization in ion exchange membranes beyond ensemble-averaged X-ray scattering is underrepresented, likely in part due to ionization damage limitations in soft materials. Here, in this study, we resolve the nanometer-size crystallites in semicrystalline ion exchange membranes by applying cryogenic four-dimensional scanning transmission electron microscopy (cryo-4D-STEM) along with data-processing algorithms designed to optimize signals at a low dose to minimize radiation damage. We investigate the effects of synthesis components, including molecular weight and thermal treatment, on a model system of AAEMs in comparison to Nafion, the most commonly used and commercially successful PEM today. We find that excess water uptake in polymer membranes, a property directly associated with weak mechanical durability and with possible negative impacts on ion conductivity, can be reduced by over 30% by varying the polymer's crystalline morphology through changes in synthesis parameters such as molecular weight and thermal history. Our results indicate that this improvement is correlated with smaller crystalline domains with a more homogeneous distribution. More broadly, these results demonstrate how the crystalline architecture of polymer membranes can be tuned through their chemistry and thermal treatment in order to improve their conductivity and durability for commercial fuel cell performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self-aligned concentrating immersion-lens arrays for patterning and efficiency recovery in scaffold-reinforced perovskite solar cells

In contrast to existing silicon, CIGS, and multi-junction cells that exhibit remarkable mechanical durability, perovskite solar cells have been shown to delaminate when subjected to the mechanical loads that occur during processing and field exposures, limiting their potential as a reliable solar technology. Mechanical reinforcement is thus essential for durable and reliable perovskite technologies. One current strategy to overcome the thermomechanical fragility of perovskite solar cells is to extrinsically shield them by introducing reinforcing scaffolds which partition the cell into many distinct microcells, but improvements in mechanical stability coincide with a reduced device efficiency due to parasitic absorption by the scaffold. We address this reduced efficiency by integrating concentrating immersion-lens arrays (CILAs) into scaffold-reinforced solar cells. These scaffolds are lithographically patterned by a maskless process, in which ultraviolet light is used to pattern the scaffolds through the CILAs, ensuring self-alignment and optical contact with the microcells. Perovskite devices are deposited into the microcells, and during operation, light is concentrated into the microcells and away from the insulating scaffolds, resulting in mechanically resilient solar cells with efficiencies comparable to planar devices. The CILAs also exhibit passive tracking of incident light—verified experimentally and with ray-tracing simulations—which is critical for optimal power output as the sun moves across the sky during the day. The simplicity of the fabrication process and the efficiency of the resulting scaffolded devices show that a lens-integrated scaffold-reinforced structure is a potential pathway to high-performance, robust, commercially viable perovskite solar cells.

14 SOLAR ENERGY↗

The first experimental evidence for improved nanomechanical properties of calcium silicate hydrate by polycarboxylate ether and graphene oxide

Graphene oxide (GO) efficiently enhances macroscale mechanical properties of cement-based materials. Yet the nanoscale reinforcing mechanism of GO for calcium silicate hydrate (C-S-H), the key binding phase of concrete, remains poorly understood. Moreover, how polycarboxylate ether (PCE)-based superplasticizers affect the nanomechanical properties of C-S-H remains unclear. The intrinsic mechanical properties of the nanocomposites are measured using high-pressure X-ray diffraction. The influences of GO and PCE on the local Ca and Si environments are probed using X-ray absorption spectroscopy. For the first time, we evidence that PCE-induced well-dispersed GO nanoplatelets strengthen the C-S-H basal planes, whereas poorly water-dispersed GO weakly interacts with basal planes and does not strengthen in plane Casingle bondO bonds. Both PCE and GO only slightly strengthen C-S-H's c-axis. Here, the bulk modulus of C-S-H/PCE/GO nanocomposite is 190% than pure C-S-H. Functional groups of PCE and GO prefer interacting with the Casingle bondO sheets of C-S-Hs instead of silicate tetrahedra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preparation, mechanical properties, and toughening mechanisms of SiCw/SiCp‐reinforced zirconia‐toughened alumina ceramics

ABSTRACT Zirconia‐toughened alumina (ZTA) ceramics with high mechanical properties were sintered by hot‐pressing method using SiC particles (SiCp) and SiC whiskers (SiCw) as the reinforcing agents simultaneously. The influences of sintering temperature, SiCp, and SiCw contents on the microstructure and mechanical properties of ZTA ceramics were investigated. It was found that both SiCp and SiCw could contribute to grain refinement significantly and promote the mechanical properties of the ceramics. However, the excess addition of SiCp or SiCw led to the formation of pores with large sizes and degraded the mechanical properties instead. When 13 wt% SiCp was introduced, the maximum flexural strength of 1180.0 MPa and fracture toughness of 15.9 MPa·m 1/2 were obtained, whereas the maximum flexural strength of 1314.0 MPa and fracture toughness of 14.7 MPa·m 1/2 were achieved at 20 wt% SiCw. Interestingly, the simultaneous addition of SiCp and SiCw could further improve the mechanical properties, and the highest flexural strength of 1334.0 MPa and fracture toughness of 16.0 MPa·m 1/2 were achieved at a SiCw/SiCp ratio of 16/4. The reinforcement mechanisms in the ceramics mainly included the phase transformation toughening of ZrO 2 , the crack deflection and bridging of SiCp and SiCw, and the pull‐out of SiCw.

Liu, Longyang↗

Strong, ductile, and hierarchical hetero-lamellar-structured alloys through microstructural inheritance and refinement

The strength−ductility trade-off exists ubiquitously, especially in brittle intermetallic-containing multiple principal element alloys (MPEAs), where the intermetallic phases often induce premature failure leading to severe ductility reduction. Hierarchical heterogeneities represent a promising microstructural solution to achieve simultaneous strength−ductility enhancement. However, it remains fundamentally challenging to tailor hierarchical heterostructures using conventional methods, which often rely on costly and time-consuming processing. Here, we report a multiscale microstructural inheritance and refinement strategy to process “structural hierarchy precursors” in as-cast heterogeneous Al 0.7 CoCrFeNi MPEAs, which lead directly to a hierarchical hetero-lamellar structure (HLS) after simple rolling and annealing. Interestingly, it takes only 10 min of annealing time, two orders of magnitude less than that required to render the state-of-the-art properties during conventional processing of Al 0.7 CoCrFeNi, for us to achieve record-high strength−ductility combinations via the hierarchical HLS design that sequentially stimulates multiple unusual deformation and reinforcement mechanisms. In particular, the HLS-enabled high hetero-deformation-induced (HDI) internal stress triggers profuse <111>-type dislocations on over five independent slip systems in the supposedly brittle intermetallic phase and activates extensive stacking faults (SFs) and nanotwinning in the adjoining soft phase with a rather high SF energy. These unexpected, dynamically reinforcing hetero-deformation mechanisms across multiple length scales facilitate high sustained HDI strain hardening, along with a salient microcrack-mediated extrinsic ductilization effect, suggesting that the proposed microstructural inheritance and refinement strategy provides an efficient, fast, and low-cost approach to overcome the strength−ductility trade-off in a broad range of structural materials.

Science & Technology - Other Topics↗